CN1635010A - Macromolecular bactericide and method for preparation - Google Patents

Macromolecular bactericide and method for preparation Download PDF

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CN1635010A
CN1635010A CN 200310122461 CN200310122461A CN1635010A CN 1635010 A CN1635010 A CN 1635010A CN 200310122461 CN200310122461 CN 200310122461 CN 200310122461 A CN200310122461 A CN 200310122461A CN 1635010 A CN1635010 A CN 1635010A
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chloride
described preparation
sterilant
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CN1286878C (en
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刘杰
李本高
汪燮卿
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

A macromolecule bactericide has the following structure: as shown in the right formula, HP represents the frame of hyperbranched polymers, n is an integer between 1 and 8, z is the result of 2n+1, R is -O-CO-CH2-CH2-CH2-, -O-CO-CH2-CH2-, -O-CO-CH2-, -O-CO-NH-CH2-CH2-CH2-, -O-CO-NH-CH2-CH2- or -O-CO-NH-CH2-, Y is an alkyl whose carbon atom number is between 1 and 30, A and B are alkyls whose carbon atom number is between 1 and 4, X is an anion selected from Cl-,Br-,I-,NO3-,ClO4-,ClO3-. The macromolecule bactericide provided by the invention can be obtained by quaternised modification of the end hydroxyl group of hyberbranched polymers. Compared with the quaternary ammonium salt bactericide, the bactericide has better effect to kill microbe when used for water containing system, its capability of killing Gram-negative bacteria is ten times as strong as that of the dodecyl trimethyl ammonium chloride.

Description

A kind of polymer sterilant and preparation method thereof
Technical field
The present invention relates to a kind of water conditioner, exactly, is a kind of polymer sterilant of suppressing aqueous system microbial contamination and preparation method thereof that is used to.
Technical background
Since quaternary ammonium salt that nineteen thirty-five fritz Domak G finds to contain chain alkyl had fungicidal activity, the synthetic of cationic germicide was one of relatively more active field of sterilant research always.At present, cationic germicide has been widely used in the bacterium algae control in industry and the domestic use of water treating processes, the sterilization and disinfection in fields such as medical treatment, health.Often use a kind of sterilant, microorganism can develop immunity to drugs, and old friends are at the sterilant of synthetic new texture constantly, and efficient bactericidal property fast also is that people expect that new type bactericide has.
In recent years, development along with polymer chemistry, novel molecular dimension having occurred is nano level branching polymer (Dendritic polymers), and it comprises dendrimer (Dendrimers) and hyperbranched polymer (Hyperbranched Polymers).Dendrimer is complete branching, and has regular geometric shape, and preparation process such as the building-up reactions and the separation of purifying are extremely complicated.The degree of branching of hyperbranched polymer is low than dendrimer, does not also have dendrimer regular geometric shape like that, but is easy to synthesize, and its production cost is significantly less than dendrimer.Compare with traditional linearity or branched polymer, the branching polymer has tangible characteristics, promptly has very many surface functional groups in the space closely at one.
U.S. Pat 006440405B1 has reported and has carried out quaternised modified to the PPI dendrimer, the quaternary ammonium modifier that contains 12 carbon atom long-chain alkyls, bactericidal property is better than corresponding monomer small molecules sterilant Dodecyl trimethyl ammonium chloride (trade names 1231), the raising of performance ascribes the molecular structure of dendrimer to, one closely in the space, the molecule outside surface contains a large amount of quaternary ammonium functional group, and positive surface charge density improves greatly.But dendrimer is a Laboratory Production, and it costs an arm and a leg, and is difficult for using in a large number as industrial goods.
World patent WO 0112725 has reported the mixture preparation of sterilant such as curable hyper-branched polyester and trichlorophenol.As antimicrobial solid material, demonstrate effect preferably with this mixture.
Up to the present, it is still rare directly hyperbranched polymer to be carried out the report of modification synthesis of super branched polymer bactericide.Major cause is that just in the last few years, people just on the basis of its structure singularity of understanding, carried out modification with the preparation high performance material to its end group, and the method great majority of modification are to be used as ultraviolet photocureable material, as U.S. Pat 005834118A.In addition, can realize that the hyperbranched polymer of suitability for industrialized production is also few, have only Sweden Perstorp company to realize suitability for industrialized production, its price is significantly less than dendrimer.
Summary of the invention
The object of the present invention is to provide a kind of low cost, high performance novel high polymer water treatment biocide.
Another object of the present invention is to provide the preparation method of above-mentioned polymer sterilant.
The structural formula of polymer sterilant provided by the invention is:
Figure A20031012246100051
Wherein HP represents the skeleton of hyperbranched polymer, the skeleton of preferred hyper-branched polyester.N is the algebraically of hyperbranched polymer, and the reaction repeated number of times when promptly hyperbranched polymer is synthetic can be 1～8, preferred 2～6 integer.Part in the bracket is represented the end group of hyperbranched polymer, and z is the quantity of end group in each molecule, and along with the increase of algebraically n, the quantity z of end group also increases, and theoretical value is 2 N+2, but because the branch degree of hyperbranched polymer can not reach 100%, so the actual end group number of each molecule is less than theoretical value.R is the skeleton of hyperbranched polymer and the connection portion between the modification group, can be-O-CO-CH 2-CH 2-CH 2-,-O-CO-CH 2-CH 2-,-O-CO-CH 2-,-O-CO-NH-CH 2-CH 2-CH 2-,-O-CO-NH-CH 2-CH 2-,-O-CO-NH-CH 2-, preferred-O-CO-CH 2-CH 2-CH 2-,-O-CO-CH 2-CH 2-,-O-CO-CH 2-.Y is that carbonatoms is 1 to 30, preferred 8 to 16 alkyl, and A and B are alkyl, carbon atom quantity is 1 to 4, can be identical or inequality, preferred A and B are methyl entirely.X represents the negatively charged ion of this sterilant, can be Cl -, Br -, I -, NO 3 -, ClO 4 -, ClO 3 -Deng acid ion, preferred Cl -, Br -, I -These negatively charged ion can the phase double replacement in water.
Polymer sterilant provided by the invention is that the terminal hydroxyl group to hyperbranched polymer carries out quaternised modified obtaining, and the preparation method comprises:
(1) with hyperbranched polymer and halogen acyl chloride in the presence of solvent and catalyzer in 0～80 ℃, preferred 20～60 ℃ are reacted.Reaction times can be 1～72 hour, preferred 12～24 hours.The mol ratio of halogen acyl chloride and hyperbranched polymer terminal hydroxyl number is 1～4: 1, preferred 2: 1.
Said hyperbranched polymer is that end group is the hyperbranched polymer of hydroxyl, preferred hyper-branched polyester, and algebraically can be 1～8, preferred 2～6.
Said halogen acyl chloride can be chloroacetyl chloride, chlorpromazine chloride, chlorobutanoylchloride, bromoacetyl chloride, bromo propionyl chloro, bromobutanoylchloride, monoiodo-acetic chloride, propidium jodiole chlorine, iodine butyryl chloride etc., preferred chloroacetyl chloride, chlorpromazine chloride, chlorobutanoylchloride.
Said solvent is non-proton type polar solvent, as tetrahydrofuran (THF), acetone, dioxane, dimethyl sulfoxide (DMSO), dimethyl formamide etc.The consumption of solvent is can the dissolved solids raw material being minimum value.
Said catalyzer is the catalyzer of organic bases, as pyridine, N, and accelerine, 4-Dimethylamino pyridine etc.Catalyzer and hyperbranched polymer terminal hydroxyl number mol ratio be 1～4: 1, preferred 2: 1.With the chlorobutanoylchloride is example, and this step reaction formula is as follows:
Figure A20031012246100061
(2) with (1) gained intermediate product and aliphatic tertiary amine in the presence of solvent in 30～120 ℃, carry out quaterisation under preferred 60～90 ℃.Reaction times can be 1～100 hour, and preferred 24～72 hours, the quaternary ammonium modifier that obtains was final product.Aliphatic tertiary amine and intermediate product the mol ratio of chloride element be 1～4: 1, preferred 2: 1.
Said aliphatic tertiary amine is the trialkyl tertiary amine that contains a long carbochain and two short-chain branchs, and structural formula is C mH 2m+1N (C fH 2f+1) 2, wherein m is 8～18 integer, and f is 1～4 integer, and preferred f is 1.
Said solvent is non-proton type polar solvent, as dioxane, dimethyl sulfoxide (DMSO) etc.The consumption of solvent is a minimum value can dissolve intermediate product.
The tertiary amine that with the short-chain branch is methyl is an example, and this step reaction formula is as follows:
Figure A20031012246100062
The prepared polymer sterilant of the present invention is easy to dissolve in water, can be used to suppress the aqueous system microbiological contamination, as the sterilization algae removal of recirculated cooling waters such as oil, chemical industry, metallurgy, thermal power generation, central air-conditioning, also can be used for the sterilization and disinfection in fields such as medical treatment, health.The said quaternary ammonium salt-modified hyperbranched polymer sterilant of the present invention is compared with quaternary ammonium salt bactericide, is used for aqueous system and has better killing microorganisms effect, and the ability of killing Gram-negative bacteria is 10 times of Dodecyl trimethyl ammonium chloride.
Description of drawings
Fig. 1 is a chlorobutanoylchloride 13C NMR spectrogram.
Fig. 2 is raw material BoltornH20's 1H NMR spectrogram.
Fig. 3 is an intermediate product (HP2Cl) 1H NMR spectrogram.
Fig. 4 is a final product (HP2N12) 1H NMR spectrogram.
Fig. 5 is raw material BoltornH20's 13C NMR spectrogram.
Fig. 6 is an intermediate product (HP2Cl) 13C NMR spectrogram.
Fig. 7 is a final product (HP2N12) 13C NMR spectrogram.
Fig. 8 is the sterilization evaluation design sketch of HP3N12 to streptococcus aureus.
Fig. 9 is the sterilization evaluation design sketch of HP3N12 to colon bacillus.
Figure 10 is the sterilization evaluation design sketch of 1231 pairs of streptococcus aureuses of small molecules quaternary ammonium salt bactericide.
Figure 11 is the sterilization evaluation design sketch of 1231 pairs of colon bacillus of small molecules quaternary ammonium salt bactericide.
Embodiment
The hyperbranched polymer that uses among the embodiment is the hyper-branched polyester of being produced by Sweden Perstorp company, and 3 series such as BoltornH20, Boltorn H30 and Boltorn H40 are arranged.The weight-average molecular weight of s-generation hyper-branched polyester Boltorn H20 is 2100g/mol, and the actual hydroxyl value of molecular end is 519mgKOH/g; The weight-average molecular weight of third generation hyper-branched polyester BoltornH30 is 3500g/mol, and the actual hydroxyl value of molecular end is 488mgKOH/g; The weight-average molecular weight of the 4th generation hyper-branched polyester Boltorn H40 is 5100g/mol, and the actual hydroxyl value of molecular end is 486mgKOH/g.
The polymer sterilant of the present invention's preparation represents that with HPnNy (wherein n represents the algebraically of hyper-branched polyester, and y represents the carbon number of alkyl chain Y) raw material is represented with HPnCl through the intermediate product that the chlorobutanoylchloride modification obtains.
Synthetic polymer sterilant HPnNy of institute of the present invention and intermediate product HPnCl, structure is all confirmed by the NMR sign. 1H, 13C NMR measures with Inova500, makees solvent with deuterium band dimethyl sulfoxide (DMSO) (DMSO-D6), the tetramethylsilane calibration.Concentration is that 0.1% solution is used for 1H NMR analyzes, and concentration is that the solution of 10-20% is used for 13CNMR analyzes.
Because three kinds of raw material Boltorn H20, Boltorn H30 the same with the characteristic peak of final product HPnNy when NMR characterizes with Boltorn H40 and intermediate product HPnCl (when n and y variation) are so only carry out the explanation of NMR sign with the example that synthesizes of HP2N12.The invention will be further described below by embodiment, but therefore do not limit the present invention.
Embodiment 1
Present embodiment is the preparation of chlorobutanoylchloride.
In 3 mouthfuls of round-bottomed flasks of churned mechanically 150mL are housed, add 40mL sulfur oxychloride and 3g Zinc Chloride Anhydrous, start stirring, add the 38mL gamma-butyrolactone fast and make solution temperature be elevated to 45 ℃.Reaction mixture is heated to 55 ℃, stirring reaction 22 hours.Supernatant liquid is transferred to and is rotated vacuum-evaporation in the round-bottomed flask of 150mL and separates, and at residual voltage 3mmHg, under 80 ℃ of the temperature unreacted raw material is steamed, and the liquid that obtains is chlorobutanoylchloride.
13CNMR (Fig. 1) characterizes and following characteristic peak: δ 173.20 (ClCOCH only occur 2CH 2CH 2Cl), δ 46.43 (ClCOCH 2CH 2CH 2Cl), δ 27.8 (ClCOCH 2CH 2CH 2Cl), δ 44.53 (ClCOCH 2CH 2CH 2Cl), illustrate and obtained chlorobutanoylchloride.
Embodiment 2
Present embodiment is the preparation of intermediate product HP2Cl.
In 3 mouthfuls of round-bottomed flasks of churned mechanically 250mL are housed, add 100mL tetrahydrofuran (THF) and 20.0g BoltornH20, start stirring, wait solid dissolving back to add the 29.9mL pyridine.Under ice-water bath, slowly drip the 41.5mL chlorobutanoylchloride, at room temperature reacted after dripping 24 hours, reaction mixture is poured in the 1L deionized water, there is brown sticky solid to separate out, again this precipitate is dissolved in the acetone, pours in the 1L deionized water, carry out repeatedly 3 times.The brown sticky solid that obtains is at residual voltage 3mmHg, carries out vacuum-drying under 80 ℃ of the temperature.Obtain 29.5g product (yield 75.0%).Through ultimate analysis, product contains Cl 16.60% (weight).
From 1H NMR analyzes as can be known, two hydroxyl characteristic peaks of raw material Boltorn H20 (Fig. 2), δ 4.94 (CH 2OH) and δ 3.46 (CH 2OH), and after the chlorobutanoylchloride modification (product HP2Cl, Fig. 3) completely dissolve, and δ 3.64 (COCH appear 2CH 2CH 2Cl) and δ 1.91 (COCH 2CH 2CH 2Cl), δ 2.43 (COCH 2CH 2CH 2Cl), illustrate chlorobutanoylchloride to the terminal hydroxyl modified-reaction of raw material carry out fully.From 13C NMR analyzes as can be known, raw material Boltorn H20 (Fig. 5) after the chlorobutanoylchloride modification (product HP2Cl, Fig. 6), δ 65.0 (CH 2OH) characteristic peak disappears, and δ 45.4 (COCH occur 2CH 2CH 2Cl), δ 28.5 (COCH 2CH 2CH 2Cl) and δ 31.9 (COCH 2CH 2CH 2Cl) characteristic peak illustrates that also the terminal hydroxyl of raw material is replaced by the chloro ester fully.
Embodiment 3
Present embodiment is the preparation of final product HP2N12.
In 3 mouthfuls of round-bottomed flasks of churned mechanically 150mL are housed, add 30.0mL dimethyl sulfoxide (DMSO) and 5.0gHP2Cl, start stirring, wait solid dissolving back to add 12.6mL dodecyl dimethyl tertiary amine (Jiangsu circle in the air chemical company limited product).80 ℃ of reactions 48 hours, behind the cool to room temperature, reaction mixture is poured in the 300mL acetone, there is the light brown solid to separate out, again this precipitate is dissolved in the ethanol, pour in the 300mL acetone, carry out repeatedly 3 times.The brown solid that obtains is at residual voltage 3mmHg, carries out vacuum-drying under 80 ℃ of the temperature, obtains 6.3g product (yield 63.0 weight %).Through ultimate analysis, product contains N 3.22% (weight).
From 1H NMR analyzes as can be known, and (product HP2N12, Fig. 4), δ 3.64 characteristic peaks of HP2Cl (Fig. 3) disappear, and δ 3.05 (CH occur behind the quaterisation 2NCH 2C 10H 20CH 3), δ 1.23 (NCH 2C 10H 20CH 3), δ 0.84 (NCH 2C 10H 20CH 3) and δ 1.65 (NCH 3), it is thorough to illustrate that quaterisation carries out.From 13C NMR analyzes as can be known, behind the quaterisation (product HP2N12, Fig. 7), the δ 45.4 of HP2Cl (Fig. 6), δ 28.5 characteristic peaks disappear, and following spectral line occurs:
δ64.0(COCH 2CH 2CH 2NCH 2C 10H 20CH 3)、
δ62.7(COCH 2CH 2CH 2NCH 2C 10H 20CH 3)、
δ22.0～31.0(COCH 2CH 2CH 2NCH 2C 10H 20CH 3)、
δ15.1(COCH 2CH 2CH 2NCH 2C 10H 20CH 3)
δ51.1(COCH 2CH 2CH 2NCH 2C 10H 20CH 3)。
Quaternised modified carrying out fully is described.
Embodiment 4
Present embodiment is the preparation of intermediate product HP3Cl.
Take by weighing 20g Boltorn H30,28.2mL pyridine, 39.0mL chlorobutanoylchloride respectively, the 90.0mL dimethyl sulfoxide (DMSO), 50 ℃ were reacted 12 hours down, and other operation steps obtains 27.8g product (yield 72.8%) according to embodiment 2.Through ultimate analysis, product contains Cl 16.08%.
Embodiment 5
Present embodiment is the preparation of final product HP3N8.
Take by weighing the product, 25.0mL dioxane, 11.0mL eight alkyl dimethyl tertiary amide (Jiangsu circle in the air chemical company limited product) of 5.0g embodiment 4 respectively, 60 ℃ of reactions 72 hours, other operation steps obtains 4.7g product (yield 54.8%) according to embodiment 3.Through ultimate analysis, product contains N 3.67%.
Embodiment 6
Present embodiment is the preparation of final product HP3N10.
Take by weighing the product, 10.9mL ten alkyl dimethyl tertiary amide (Jiangsu circle in the air chemical company limited product) of 5.0g embodiment 4 respectively, 90 ℃ of reactions 24 hours, other operation steps obtained 5.1g product (yield 55.0%) according to embodiment 3.Through ultimate analysis, product contains N 3.40%.
Embodiment 7
Present embodiment is the preparation of final product HP3N12.
Take by weighing the product, 12.2mL dodecyl dimethyl tertiary amine (Jiangsu circle in the air chemical company limited product) of 5.0g embodiment 4 respectively, operation steps obtains 5.7g product (yield 58.1%) according to embodiment 3.Through ultimate analysis, product contains N 3.17%.
Embodiment 8
Present embodiment is the preparation of final product HP3N14.
Take by weighing the product, 13.7mL tetradecyl dimethyl tertiary amine (Jiangsu circle in the air chemical company limited product) of 5.0g embodiment 4 respectively, 80 ℃ of reactions 72 hours, other operation steps obtained 6.3g product (yield 60.0%) according to embodiment 3.Through ultimate analysis, product contains N 2.98%.
Embodiment 9
Present embodiment is the preparation of final product HP3N16.
Take by weighing the product, 15.2mL hexadecyldimethyl benzyl ammonium tertiary amine (Jiangsu circle in the air chemical company limited product) of 5.0g embodiment 4 respectively, 90 ℃ of reactions 48 hours, other operation steps obtained 7.1g product (yield 63.9%) according to embodiment 3.Through ultimate analysis, product contains N 2.81%.
Embodiment 10
Present embodiment is the preparation of intermediate product HP4Cl.
Take by weighing 20.0g Boltorn H40,21.2g 4-Dimethylamino pyridine, 38.8mL chlorobutanoylchloride, 100mL dimethyl formamide respectively, reaction is 12 hours under the room temperature, and other operation steps obtains 26.8g product (yield 70.3%) according to embodiment 2.Through ultimate analysis, product contains Cl 16.00%.
Embodiment 11
Present embodiment is the preparation of final product HP4N12.
Take by weighing the product, 12.2mL dodecyl dimethyl tertiary amine (Jiangsu circle in the air chemical company limited product) of 5.0g embodiment 10 respectively, 90 ℃ of reactions 48 hours, other operation steps obtained 5.2g product (yield 53.0%) according to embodiment 3.Through ultimate analysis, product contains N 3.14%.
Embodiment 12
Present embodiment is the fungicidal activity evaluation to the heterotrophic bacteria hybrid bacterial strain.
The final product that embodiment 3,5,6,7,8,9,11 is obtained carries out the sterilization effect evaluation, chooses commercially available small molecules quaternary ammonium salt bactericide Dodecyl trimethyl ammonium chloride (be called for short 1231, chemical company limited product circles in the air in Jiangsu) simultaneously as a comparison.Evaluation result sees Table 1, table 2.
The fungicidal activity evaluation is carried out according to chapter 2 " microbiological test method " in China PetroChemical Corporation's " water coolant analysis and test method ".Concentration of sterilant is for containing N +380 μ M, act on 4 hours, contain 13 kinds of bacterial strains in the bacteria suspension, be respectively: streptococcus aureus (AS1.2465), bacillus subtilis black variety gemma bacterium sheet (AS1.3343), Bacillus licheniformis (AS1.521), Sarcina lutea (AS1.880), five kinds of gram positive bacterial strains such as subtilis (AS1.1849) and colon bacillus (AS1.2021), Pseudomonas stutzeri (AS1.1803), Aeromonas hydrophila (AS1.1816), acinetobacter calcoaceticus (AS1.2004), Alcaligenes faecalis (AS1.2006), enteroaerogen (AS1.2021), Pseudomonas aeruginosa (AS1.2464) Fu Shi citric acid bacterium eight kinds of gram negative strains such as (AS1.1732).
From table 1, table 2 as can be seen, various polymer sterilant provided by the present invention, the effect of killing 13 kinds of heterotrophic bacterium hybrid bacterial strains is better than 1231.
Sterilizing rate adopts following formula to calculate.
Table 1
Blank 1231 examples, 7 examples of sterilant 3 examples 11
Bacterial count (individual/milliliter) 5.8 * 10 61.6 * 10 55.5 * 10 47.5 * 10 41.0 * 10 5
Sterilizing rate 97.241% 99.052% 98.707% 98.276%
Table 2
Blank example 5 examples of sterilant 6 examples 7 examples 8 examples 9
Bacterial count (individual/milliliter) 2.0 * 10 71.0 * 10 48.0 * 10 42.0 * 10 55.5 * 10 58.0 * 10 5
Sterilizing rate 99.950% 99.600% 99.000% 97.250% 96.000%
Embodiment 13
Present embodiment is the fungicidal activity evaluation to single bacterial strain, and assessment method carries out according to embodiment 12.
The final product HP3N12 that embodiment 7 is obtained kills the effective evaluation of streptococcus aureus, colon bacillus, choose commercially available small molecules quaternary ammonium salt bactericide Dodecyl trimethyl ammonium chloride (be called for short 1231, chemical company limited product circles in the air in Jiangsu) simultaneously as a comparison.Evaluation result is seen Fig. 8, Fig. 9, Figure 10, Figure 11.
From Fig. 8, Fig. 9, Figure 10, Figure 11 as can be seen, compare with 1231, polymer sterilant HP3N12 provided by the present invention has efficiently characteristics fast when killing streptococcus aureus, colon bacillus.For quantificational expression HP3N12 and 1231 in the difference of killing aspect the colon bacillus, elite when being taken at certain hour and reaching identical sterilizing rate the concentration of required sterilant compare.When 2h killed 50% colon bacillus, the nitrogen ionic concn of HP3N12 was 3.8 μ M, and 1231 nitrogen ionic concn is 38 μ M; When killing 90% bacterium, the nitrogen ionic concn of HP3N12 is 38 μ M, and 1231 nitrogen ionic concn is 380 μ M.Therefore can think that the ability that HP3N12 kills colon bacillus is 1231 10 times.

Claims (12)

1. polymer sterilant has following structure:
Wherein HP represents the skeleton of hyperbranched polymer, and n is 1～8 integer, and z is 2 N+2, R is-O-CO-CH 2-CH 2-CH 2-,-O-CO-CH 2-CH 2-,-O-CO-CH 2-,-O-CO-NH-CH 2-CH 2-CH 2-,-O-CO-NH-CH 2-CH 2-or-O-CO-NH-CH 2-, Y is that carbonatoms is 1～30 alkyl, and A and B are that carbonatoms is 1～4 alkyl, and X is selected from Cl -, Br -, I -, NO 3 -, ClO 4 -, ClO 3 -In negatively charged ion.
2. according to the described sterilant of 1 claim 1, it is characterized in that HP represents the skeleton of hyper-branched polyester, n is 2～6 integer.
3. according to the described sterilant of 1 claim 1, it is characterized in that R is-O-CO-CH 2-CH 2-CH 2-,-O-CO-CH 2-CH 2-or-O-CO-CH 2-, Y is that carbonatoms is 8～16 alkyl, and A and B are methyl, and X is selected from Cl -, Br -, I -
4. the preparation method of the described polymer sterilant of claim 1 comprises:
(1) be that the algebraically of hydroxyl is that 1～8 hyperbranched polymer and halogen acyl chloride react in 0～80 ℃ in the presence of polar solvent and organic alkali catalyst with end group, collect intermediate product, the mol ratio of halogen acyl chloride and hyperbranched polymer terminal hydroxyl number is 1～4: 1;
(2) (1) gained intermediate product and aliphatic tertiary amine are carried out quaterisation in the presence of polar solvent under 30～120 ℃, collect final product, aliphatic tertiary amine and intermediate product the mol ratio of chloride element be 1～4: 1.
5. according to the described preparation method of claim 4, it is characterized in that (1) step temperature of reaction is 20～60 ℃, the reaction times is 1～72 hour, and (2) step temperature of reaction is 60～90 ℃, and the reaction times is 1～100 hour.
6. according to the described preparation method of claim 4, it is characterized in that said hyperbranched polymer is that end group is the hyper-branched polyester of hydroxyl, algebraically is 2～6.
7. according to the described preparation method of claim 4, it is characterized in that, said halogen acyl chloride is selected from a kind of in chloroacetyl chloride, chlorpromazine chloride, chlorobutanoylchloride, bromoacetyl chloride, bromo propionyl chloro, bromobutanoylchloride, monoiodo-acetic chloride, propidium jodiole chlorine, the iodine butyryl chloride, or two or more mixture wherein.
8. according to the described preparation method of claim 7, it is characterized in that said halogen acyl chloride is selected from chloroacetyl chloride, chlorpromazine chloride and chlorobutanoylchloride, or two or more mixture wherein.
9. according to the described preparation method of claim 4, it is characterized in that said solvent is non-proton type polar solvent.
10. according to the described preparation method of claim 9, it is characterized in that said solvent is tetrahydrofuran (THF), acetone, dioxane, dimethyl sulfoxide (DMSO) or dimethyl formamide.
11., it is characterized in that said organic alkali catalyst is pyridine, N according to the described preparation method of claim 4, accelerine or 4-Dimethylamino pyridine, catalyzer and hyperbranched polymer terminal hydroxyl number mol ratio be 1～4: 1.
12., it is characterized in that said aliphatic tertiary amine structural formula is C according to the described preparation method of claim 4 mH 2m+1N (C fH 2f+1) 2, wherein m is 8～18 integer, f is 1～4 integer.
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CN104974230A (en) * 2015-08-05 2015-10-14 中国科学技术大学 Antibacterial star-shaped polypeptide as well as preparation method and application thereof
CN105085905A (en) * 2015-08-05 2015-11-25 中国科学技术大学 Preparation method of anti-microbial star type poly-polypeptide
CN106084203A (en) * 2016-06-20 2016-11-09 苏州睿研纳米医学科技有限公司 A kind of water soluble block polyquaternary ammonium salt macromolecular material and preparation method thereof
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CN101886333A (en) * 2010-03-05 2010-11-17 东华大学 Hyperbranched polyester quaternary ammonium salt and base reduction promoter and application thereof
CN104974230A (en) * 2015-08-05 2015-10-14 中国科学技术大学 Antibacterial star-shaped polypeptide as well as preparation method and application thereof
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